Carbamoyl disulfides in fungicidal and herbicidal methods



United States Patent 14 Claims. (ci. 71-2.7

The present invention relates to known carbamoyl disulfides which showremarkable fungicidal activity and can also be used to destroy waterplants.

Carbamoyl disulfides have already repeatedly been described in theliterature without data as to their applicability. For their production,according to the disclosures of Am. Soc. 82, p. 155 (1960), and 82, p.5106 (1960), three different routes are possible, which, are listed inthe following general scheme:

It has been found that the known carbamoyl disulfides of the followingformula which is also mentioned above in which R and R stand forhydrogen and for alkyl, alkenyl, cycloalkyl and aryl which radicals maybe substituted by halogen or a further carbamoyl disulfide group,

R and R taken together with the nitrogen atom stand for a heterocyclicradical with 5 to 6 ring members, and

R stands for alkyl and aryl which radicals may be substituted by halogenand nitro groups,

possess a high fungicidal activity and can also be used to destroyplants growing in water.

In the above mentioned Formula I of the products according to theinvention R and R preferably stand for hydrogen, alkyl groups with 1 to4 carbon atoms, alkenyl groups with 1 to 4 carbon atoms, cycloalkylgroups with 5 to 6 carbon atoms and phenyl. These groups can besubstituted by halogen and a further carbamoyl disulfide group. R and Rtaken together with the nitrogen atom preferably stand for pyrrolidineand morpholine radicals. R preferably stands for alkyl with 1 to 4carbon atoms and phenyl. These radicals can be further substituted byhalogen and the nitro group.

Suitable compounds which can be employed as plant protection agents aree.g. carbamoyl-trichloromethyldisulfide, Nmethylcarbamoyl-fluorodichloromethyldisulfide, N,N dimethylcarbamoylfluorodichloromethyldisulfide, N-allylcarbamoylfiuorodichloromethyldisulfide,N-phenylcarbamoyl-bromofluorochlorornethyldisulfide, N (2,4dichlorophenyl) trifluoromethyldisulfi-de, N methylcar- ICC bamoylphenyldisulfide, N,N dimethylcarbamoyl-(2- nitrophenyl) disulfide andN,N A tetramethylene-biscarbamoyltrichloromethyldisulfide) The carbamoyldisulfides to be used according to the present invention are welltolerated by plants, and possess a wide range of activity againstphytopathogenic organisms.

They are especially suitable for combating soil fungi, whichattacksubterranean plant organs or plant parts near the soil surface,preparations of the active ingredient being preferably applied as soiltreating agents, but possibly also as dressing. The carbamoyl disulfidescan be formulated to be empolyed alone or in combination with otherplant protection agents, cultivation and preparation assistants in theform of solutions, emulsions, suspensions, granules, powders or paste.

The suitability of carbamoyl disulfides for combating plant diseases isshown by the following examples of application which are given for thepurpose of illustrating the invention.

The following compounds, which are denoted by I to XI in the examples,were tested.

Q-NH-C o-s-so r01,

(VIII) nan-o os-s-oHo1oHcn The following examples are given for thepurpose of illustrating the invention.

Example 1 (A) When using the preparations as soil treating agents, theywere previously extended with talc and quartz sand to a scatterablepowder containing 1% of active ingredient. Sterilised Fruhstorf standardearth was inoculated with pure cultures of the phytopathogenic soilfungi Rhizoctonia solan'i, Fusarium culmorum, Verticillium albo-atrumand T hielzzviopsis basicola and mixed intimately with the abovementioned formulations. Sowing of pea and cotton seeds then took place.In a greenhouse the seeds were allowed to develop under optimum soilmoisture and temperatures between 18 and 25% C.

(B) When testing the preparations for their inhibiting action on themy-celium growth of phytopathogenic soil fungi, the preparations weredissolved in acetone at 0.1

and 1% concentrations and in this form added to potatodextrose-agarliquified by heating, so that the concentration of active agent in thesubstrate came to 10 and 100 mg./litre. After the substrate-active agentmixture had solidified in Petri dishes, the soil fungi to be tested wereinoculated from pure cultures in slices of 5 mm. diameter. Afterincubation for three days at 20 C. the evaluation of the myceliurngrowth or its inhibition took place.

The following results were obtained.

Active agent Ircpaconcen- Phytopathogenic soil fungi whose myceliumration tration growth was completely stopped by the active in subagentstrate, ng./litre III 100 Sclerutium, rolfsiz', Sclerotz'nz'asclrrotz'ormn, Thielaviopsis basicola, Phytop/zthora cactormn, Fusariumculmorum, Fusarium oxysporum, Fusan'um salami. IV Sclerotium rolfivii,Sclcrotinia sclerotioru'm, Thiclavz'opsz's basicolo, Phytophthoracactorum, F'usarizun culmorum. IV 100 Sclamtium rolfsii, Sclerotiniasclerotiorum, Thz'claviopsix basicula, Phytophthom cactumm, F usariu'mculmormn, and Vertz'cillium 111110. atrum, F'usarz'um oxyspor'um,Fusarimn salani. V 10 Sclcratiumrolfsii. V 100 Sclcrotium. rolfsii,Sclerotinz'a sclerotiormn, Thiclaviopsis basicoltz, Phytophthoracactorzmz, Fusarium culmorum, Fusarium org 3170mm. VI 100 Sclerotiumrolfsz'i, Sclerotz'm'a sclerotiorzmi, Thielaviopsis husicola,Phytophthora cactorum. VII -l 100 Sclerotium rolfsii, Sclcrotim'asclerotiorum, Thielaviopsis basicola, Phytophthora cllctoru-m, Fusan'mnculmoru m. VIII 100 Sclerotium rolfsii, Sclerotim'a aclerotiormn,Thielaviopsis basicola, Phytophthora cactorum, F'usarium culmorum,Fusarium osrysporu'm, Fusarium solmli. IX 100 Sclerotium rolfsii,Sclcrotinia sclerotioru'm, Thielaviopsis baszcola, Phytophthoracactorum, Fusarium culmoru m.

(C) When testing the preparations as seed dressing agents againstseed-generated disease germs, wheat was contaminated with 5% spores ofwheat rust (T illetia tritici) and applied to the seeds with thepreparations in a fine-grained mixture with tale in the usual way as adry dressin The contaminated and treated wheat grains were then exposedon moist loam under moist loose compost earth at 10 C. to optimumconditions of germination for the spores. After 10' days the wheat rustspores had taken on untreated wheat seed almost completely at about50,000 to 75,000 spores/wheat grain and were under the conditionsprevailing in practice in a position to infect the wheat seedling. Aftertreatment of the contaminated wheat grains with 300 mg. of active agentper kg. of seeds, a practically complete inhibition of spore germinationwas achieved with the preparations I, II, III, IV and IX, except forindividual spores which occasionally germinated.

Example 2 A few representatives of the class of compound according tothe invention have shown a high activity as fungicides againstFusicladium dendriticum (=Venturia inaequalis) and against Botrytiscinerea. The activity values and a brief description of the test methodsare described in the followin The examination of the fungicidal activitywas carried out:

(a) In the spore germination test on condia of F usz'cladiumdendriticum. Solutions or emulsions of the preparations are so mixedwith aqueous suspensions of the fungus spores that the preparationconcentrations given in the table result. Drops of the mixture areplaced on the object carrier and these are incubated in Petri dishesmaintained moist in the conditioning cupboard at C. for 24 hours. Amicroscopic activity determination of the state of germination is thencarried out, whereby the germination is evaluated with O=100% notgerminated, via IIlI germinated, to V:100% germinated (inactive).

g the compounds I and II of the invention.

(b) In the leaf test on separated leaves of Vicia faba with conidia ofBotrytis cine/a. In a similar way, as described above under (a),preparation-spore mixtures were produced. With these mixtures smillfilter paper discs are saturated and these are laid on the leaves ofVicia faba. Incubation in Petri dishes as described above under (a). p

48 hours after the beginning of the experiment, evaluation takes place,the formation of lesions on the leaves of 0 (:no lesions), via IH(=medium development of lesions) to V (unhibited formation oflesions=inactive) being determined.

The acitivity of the compounds according to the invention is given inthe following table.

Fusicladium dcntr. Botrytis cinema Compound 0. 0001% 0. 00005% 0. 0001%0. DOUG-5% 0 0 0 0 III IV I IV IV 0 0 0 0 Thiuram ('IM'ID) I III 0 IIIUntreated control. V V V V Example 3 The compounds according to theinvention can also be used for the destruction of plants growing inwater. 3 water plants (Elodea, Myriophyllum and Vallisneria) are allowedto grow in aqueous solutions which contain After the period of 3 weeksthe degree of destruction is determined. (0 means no eifect and 5 meansthat the plants are completely destroyed) Active Degree of destructionagent Compound amount in mg./ Elodea Mario- Vallislitre phyllum neria I10 5 5 5 5 5 5 5 2, 5 3 5 4-5 II 50 5 5 5 10 5 5 5 5 4 5 5(Etliylendipyridyliumdibromide) 5 3-4 1-2 1 We claim:

1. A method for controlling fungal infection of soil, plants and seedscomprising applying to the same an effective amount of a compound of theformula 3. A method for controlling fungal infection of soil, plants,and seeds comprising applying to the same an effective amount of acompound having the formula CH NHCO SSCFCI 4. A method for controllingfungal infection of soil,

plants, and seeds comprising applying to the same an effective amount ofa compound having the formula 5. A method for controlling fungalinfection of soil, plants, and seeds comprising applying to the same aneffective amount of a compound having the formula 6. A method forcontrolling fungal infection of soil, plants, and seeds comprisingapplying to the same an effective amount of a compound having theformula 7. A method for controlling fungal infection of soil, plants,and seeds comprising applying to the same an effective amount of acompound having the formula @NH-C o-s-s-c c 1,

8. A method for controlling fungal infection of soil, plants, and seedscomprising applying to the same an effective amount of a compound havingthe formula 9. A method for controlling fungal infection of soil,plants, and seeds comprising applying to the same an effective amount ofa compound having the formula 10. A method for controlling fungalinfection of soil, plants, and seeds comprising applying to the same aneffective amount of a compound having the formula CH NH-COS-SC-HClCCl11. A method for controlling fungal infection of soil,

. 6 v plants, and seeds comprising applying to the same an effectiveamount of a compound having the formula CH =OH-OH NHC0S-fiSCFCl 12. Amethod for controlling fungal infection of soil, plants, and seedscomprising applying to the same an effective amount of a compound havingthe formula 13. Method for controlling plant growth in water comprisingadding to said water an effective amount of a composition containing, asactive ingredient, a compound having the formula 14. Method forcontrolling plant growth in water comprising adding to said water aneffective amount of a composition containing, as active ingredient, acompound having the formula References Cited by the Examiner UNITEDSTATES PATENTS OTHER REFERENCES Journal of American Chemical Society,vol. 82, pp. -158 and 5106-5107 (1960) JULIAN S. LEVITT, PrimaryExaminer.

13. METHOD FOR CONTROLLING PLANT GROWTH IN WATER COMPRISING ADDING TOSAID WATER AN EFFECTIVE AMOUNT OF A COMPOSITION CONTAINING, AS ACTIVEINGREDIENT, A COMPOUND HAVING THE FORMULA